Reduced odor fragrance sampler

ABSTRACT

A sampler for delivery of microencapsulated liquid fragrance material is provided that comprises at least one treated paper sheet defining an enclosed cavity. The paper sheet is at least partially treated with a volatile containment treatment, wherein the volatile liquid containment treatment is water-stable and organic liquid capsule fill-stable. The enclosed cavity is substantially completely defined by treated portion(s) of the sheet. Microcapsules comprising microencapsulated organic liquid capsule fill are disposed within the cavity.

This application is a divisional application of U.S. Ser. No.08/065,643, filed May 21, 1993, now U.S. Pat. No. 5,419,958, which is acontinuation-in-part of U.S. Ser. No. 07/889,732, filed on May 28, 1992,now abandoned.

FIELD OF THE INVENTION

This invention relates to microencapsulated fragrance samplers. Moreparticularly, this invention relates to microencapsulated fragrancesprovided in a special reduced odor delivery system.

BACKGROUND

Fragrance samplers comprising a microencapsulated fragrance and at leastone binder layer between two surfaces are well known in the industry.These samplers have become a common vehicle for advertising perfumes andother fragrances through inserts in magazines and the like. Use of thesefragrance samplers has become objectionable to some consumers becausemany samplers have a tendency to prematurely release some fragrance.This premature emission may be due to accidental breakage of somemicrocapsules during the handling of the inserts or the magazinesthemselves, or may be due to the presence of non-encapsulated fragrancein the sampling device.

U.S. Pat. No. 4,925,517 discloses the use of a base coating on a surfaceto be subsequently coated with a microcapsule-bearing layer. The basecoating functions in part to control the rate and degree of penetrationof liquid from the carrier for microcapsules into the underlying paper.Typically the base coating is softened by the carrier liquid of thecapsule containing slurry as a means of controlling the bond strengthwithin the sampling device. Preferred polymers to be used in the basecoating are water-softenable or organic solvent soluble, as disclosed atcolumn 5, lines 7-15.

U.S. Pat. No. 4,988,557 discloses a similar carrier activated basecoating that is applied in a discontinuous pattern to provide separateareas of the sampler in which the capsules are ruptured when the pieceis opened, as well as regions in which the microcapsules may be freelyremoved.

U.S. Pat. No. 4,876,136 to Chang, et. al. discloses a lipstick samplingdevice that is a three layered structure to deliver a small amount oflipstick to a potential customer. The construction comprises a carriersheet, a window sheet and a cover sheet. The carrier sheet may be anyfilm or sheet material, and is preferably paper that has an oleophobicimpregnate or a barrier layer coated on one side. See column 3, lines31-37 and column 5, lines 10-32.

U.S. Pat. No. 4,878,775 to Norbury, et. al. discloses a dry liquidapplicator that is a support surface with a coating of relatively largemicrocapsules and with an overlay of a liquid permeable top protectivelayer. The bottom of the support surface is preferably not readilypenetrated by the liquid in the capsules, and is preferably completelyimpermeable to the liquid. See column 2, lines 27-33.

SUMMARY OF THE INVENTION

A sampler for delivery of microencapsulated liquid fragrance material isprovided that comprises at least one treated paper sheet defining anenclosed cavity. The paper sheet is at least partially treated with avolatile containment treatment, wherein the volatile liquid containmenttreatment is water-stable and organic liquid capsule fill-stable. Theenclosed cavity is substantially completely defined by treatedportion(s) of the sheet. Microcapsules comprising microencapsulatedorganic liquid capsule fill are disposed within the cavity.

For purposes of this invention, the volatile liquid containmenttreatment is considered water-stable or organic liquid capsulefill-stable if a piece of ordinary bond paper provided with thistreatment shows no absorption of liquid into the paper after ten minutesof exposure to a drop of water and to a drop of organic liquid capsulefill placed by an ordinary medicine dropper on the treated side of thepaper. The volatile liquid containment treatment is a polymeric solutionor emulsion that may be coated on a paper sheet in a standard coatingprocess in-line with the printing of ink on the paper, and will curein-line to provide the desired containment properties.

The problem of unwanted escape of volatile liquid capsule fill materialas experienced in the prior art is avoided by the use of a volatileliquid containment treatment on the paper forming themicrocapsule-containing cavity. Detectable odor emitting from thesampler is substantially reduced in accordance with the presentinvention. The use of this containment treatment provides an economicalsampler that can be prepared using conventional printing pressequipment. The sampler can be presented in an attractive paper formatthat is acceptable to the consumer, the manufacturer, the advertiser andeven to the person that does not desire to be exposed to the fragrancebeing presented in the sampler.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a plan view of an embodiment of the present invention, withthe adhesive defining the cavity shown in phantom.

FIG. 2 is an enlarged cross-sectional view of the embodiment shown inFIG. 1 taken along line 2--2.

FIG. 3 is a plan view of an alternative embodiment of the presentinvention, with the adhesive defining the cavity shown in phantom.

FIG. 4 is an enlarged cross-sectional view of the embodiment shown inFIG. 3 taken along line 4--4.

FIGS. 5-12 are sequential representations of steps in preparing apreferred embodiment of the present invention, wherein FIGS. 5-9 and 11are plan views and FIGS. 10 and 12 are cross-sectional views of theembodiments shown in FIGS. 9 and 11, respectively.

DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS

In the description which follows, it will be assumed that themicrocapsules contain a fragrance oil. However, it will be appreciatedthat other volatile microencapsulated liquids may be delivered in thesame manner, and similarly prevented from unwanted leakage from thesampler that may cause olfactory discomfort or inconvenience. Examplesof such materials include mineral oil microcapsules with associatedpigments which have been used in samplers for eyeshadow and othercosmetic materials.

An additional benefit that may be realized in utilizing the volatileliquid containment treatment as described herein is the ability to printink under the treatment, thus providing artwork in all areas of thesampler without fear of smearing of ink. The present volatile liquidcontainment treatment allows application of microcapsule slurries oranchoring layers that are cast from water over water-sensitive inks.Similarly, this treatment allows the use of solvent sensitive inksdirectly under a coating of solvent-containing microcapsules withoutfear of smearing of the ink when the microcapsules are fractured.

Turning now to the drawing, FIG. 1 is a plan view of embodiment 10 ofthe present invention. Paper substrate 12 is provided with a coating ofvolatile liquid containment treatment 14 at a portion of the substrate.Paper cover sheet 16 is adhered to paper substrate 12 by adhesive 18,shown in phantom.

FIG. 2 is a cross sectional view of the embodiment 10 shown in FIG. 1taken along line 2--2. Paper cover sheet 16 is adhered to papersubstrate 12 by adhesive 18, thereby defining a cavity havingmicrocapsules 20 disposed therein. The cavity may be described as beingsubstantially defined by the treated paper, because the walls of thecavity are formed by treated paper and, at one small margin, adhesive.It is contemplated that small amounts of untreated paper may form aportion of the wall of the cavity if the adhesive does not overlie thevolatile liquid containment treatment, but rather is adjacent to thetreatment. Such an embodiment may be preferred where the volatile liquidcontainment treatment is found to unattractively peel upon separation ofthe cover paper from the substrate paper sheet. Microcapsules 20 areoptionally bound to paper substrate 12 by binder 22.

FIG. 3 shows a plan view of an alternative embodiment 30 of the presentinvention, wherein paper substrate sheet 32 is provided with a coatingof volatile liquid containment treatment 34 at a portion of thesubstrate. Substrate sheet 32 is folded over to define the cavity,together with adhesive 38 shown in phantom.

FIG. 4 is a cross sectional view of the embodiment shown in FIG. 3 takenalong line 4--4. Paper substrate sheet 32 having liquid containmenttreatment 34 is folded over at line 35 to form a cover portion 36. Coverportion 36 is adhered to paper substrate sheet 32 with adhesive 38, thusdefining a cavity having microcapsules 40 disposed therein. Optionalbinder 42 adheres microcapsules 40 to paper substrate sheet 32.

FIGS. 5-12 are sequential representations of steps in preparing apreferred embodiment of the present invention. FIG. 5 is a plan view ofthe first step of this preparation, wherein release coating 53 isapplied to a predetermined zone on paper substrate sheet 52. Releasecoating 53 may be any material that preferentially causes adhesivefailure in adhesion of paper substrate sheet 52 to another piece ofpaper through an adhesive. This adhesive failure may be due to lowsurface energy of the surface as may be experienced in traditional lowadhesion backsize material such as silicone treatments or perfluorinatedtreatments or using other materials that the adhesive does not adherewell to, such as heat-set inks or varnishes. Alternatively, thepreferential adhesive failure may be due to internal fracturing ofrelease coating 53 due to poor internal cohesion of this layer.

FIG. 6 shows the next step in the method of preparing the embodiment ofthe present invention, wherein paper substrate sheet 52 and releasecoating 53 are treated with volatile liquid containment treatment 54.Preferably, this volatile liquid containment treatment is a polyvinylalcohol containing a crosslinking agent. This coating is dried andcrosslinked in a second oven.

FIG. 7 represents the next step in preparing the preferred embodiment,which comprises placing adhesive 58, such as a standard envelope glue,in a pattern over the area previously coated by release coating 53. Inthe next step, as represented in FIG. 8, microcapsules 60 are providedin an area spaced from the region defined by adhesive 58, and on top ofvolatile liquid containment treatment 54. The embodiment as shown inFIG. 8 is folded at fold line 62 to form a fully enclosed cavity asshown in FIG. 9, with adhesive 58 shown in phantom. A cross sectionalview of the embodiment shown in FIG. 9 is taken along line 10--10 isshown in FIG. 10. As represented in cross-sectional view of FIG. 10,capsules 60 are lightly bound to volatile liquid containment treatment54 by binder 64. When this embodiment is opened to sample the fragrance,adhesive 58 is transferred to the portion of paper substrate 52 on theopposite side of fold line 62 from release coating 53. This result isshown in FIG. 11, and in the cross sectional view of FIG. 12, takenalong line 12--12. Volatile liquid containment treatment 54 splits awayfrom release coating 53, thereby providing easy opening of theembodiment without paper fiber delamination or tearing. This provides anattractive piece both in the closed and open position of the sampler.

The volatile liquid containment treatment of this invention is selectedto be water-insoluble after cure, and insoluble in the selected organicliquid capsule fill that is to be used in the particular embodiment tobe constructed.

The volatile liquid containment treatment is a polymeric material thatmay be coated at rapid web speed from an organic solvent or water, andwhich forms an effective barrier to oil and water fluids that migratethrough the paper and to be sensed by persons handling the sampler ormagazines containing the sampler. Preferably, the volatile liquidcontainment treatment is impervious to liquids, but allows thetransmission of moisture vapor through the layer. Preferably, thepolymer is chemically cross-linked in situ. Alternatively, the polymermay derive its barrier properties from "virtual crosslinks" that areachieved through strong interchain attractive forces such as polymerchain entanglement, ionic interactions, crystallization, van der Wallsforces and hydrogen bonding. Entanglement of polymer chains, forexample, would likely be observed in block copolymers containing highlyphase separated domains. Similarly, polymers containing significantionic species have strong polar interactions that will provide aneffective barrier to liquids, and thus act as a volatile liquidcontainment treatment under this invention. Chemically crosslinkedpolymers that are crosslinked in situ are the preferred volatile liquidcontainment treatment material.

In accordance with this invention, the volatile liquid containmenttreatment may be applied to a paper substrate at a high web speed and atvery low cost. No additional adhesives or expensive laminationtechniques are required to achieve the desired containment of volatileliquids.

Preferably, the volatile liquid containment treatment is transparent, sothat the underlying ink is not distorted to the naked eye through thetreatment layer.

The volatile liquid containment treatment polymer preferably is castfrom an appropriate system that will not damage the image created by anyink that may underlie the portion of the paper to be treated. Thus, whenthe ink is solvent sensitive, the volatile liquid containment treatmentmust be cast only from solvents that will not dissolve or adverselyaffect the ink in the time required for the carrier to dissipate.Because most standard and economical press inks are water insoluble, theprotective polymer treatment preferably is cast from a water system,either a water solution or emulsion based. Water systems also areadvantageous because they do not contain significant quantities ofvolatile organic components that may have an adverse ecological effect.

Polymers that may be selected for use in the present invention includethe polyvinyl alcohols and copolymers thereof, urethanes, acrylatedurethanes, acrylate functional acrylate polymers, ethylenicallyunsaturated monomers, styrene-butadiene polymers, Carboset resins andthe like. The above polymers may be rendered suitable for use as avolatile liquid containment treatment in one or more ways. While all ofthe above polymers may be crosslinked by adding an appropriatecrosslinking agent to the solution before application to the paper,alternative curing methods may be utilized as will now be apparent tothe skilled artisan. For example, many of the vinylic polymers may becrosslinked by exposure to electron beam or ultraviolet radiation.Alternatively, the readily crystallizable polymers, such as thepolyvinyl alcohol polymers or copolymers, may be crystallized byexposure to heat to provide a protective barrier to liquids.

Ionic polymers, such as the Carboset resins commercially available fromB.F. Goodrich, Inc. are preferably cast from high pH solutions. As thewater evaporates and the pH decreases, the ionic attractions of thepolymers promote formation of a volatile liquid containment treatmentthat is impermeable to water and organic liquid capsule fill.

Crosslinked polyvinyl alcohol is well suited as the volatile liquidcontainment treatment of this invention as it is both readily appliedfrom aqueous solution and crosslinked by a number of commerciallyavailable agents. Cross-linking agents may be selected from thosecomponents known in the art to effect crosslinking of the polymer tomake the volatile liquid containment treatment. Examples of suchcrosslinkers useful for polyvinyl alcohol polymers are dimethylolurea,trimethylolurea, glyoxal, glutaraldehyde, oxalic acid, diepoxides,polyacrolein, dialdehyde starch, divinyl sulfone, diisocyanates,dihydroxydiphenylsulfone, various organometallic compounds such as thetitanates commercially available under the KEN-REACT Brand from KenrichPetrochemicals, Inc., the zirconium analogs to the above titanates, andother bifunctional compounds that react with hydroxyl groups.Cross-linking rate enhancers, such as peroxy catalysts, may also beemployed. Similarly, the Carboset resins may be cured by reaction withformaldehyde condensation resins, epoxy resins and multivalent metalions such as calcium, zinc, iron or aluminum.

The polymer is preferably cross-linked in situ by first adding aneffective amount of cross-linking agent to the polymer compositionbefore application to the paper. Preferably, the polymer has a pot lifeof an hour to a day before application is hampered by cross-linking. Thevolatile liquid containment treatment may be applied to the paper usingany appropriate application method, including, for example, spraying,bar coating, roll coating, extrusion coating, pad coating and curtaincoating. The thus treated paper is passed through an oven to speed upthe curing process of the volatile liquid containment treatment.Typically, the paper is passed through an oven such that the webtemperature is between 200° and 300° F., and more preferably between215°-250° F. at a web speed of 400-1000 feet/minute.

In use, the cross-linkable polymer is cast on the paper substrate at aslow a treatment weight as possible, while still affording the desiredamount of containment of volatile liquids. Generally, a treatment weightat least sufficient to avoid having void areas in the volatile liquidcontainment treatment is required. Treatment weights of between about0.3 to 1.4 lb/1300 sq ft. are preferred, with treatment weights of about0.5 to 0.9 lb/1300 sq ft. being particularly preferred.

The adhesive that may be used to adhere the treated paper sheet(s)together to form the enclosed cavity may be selected from any of theadhesives known in the art, including pressure-sensitive adhesives, hotmelt adhesives, contact adhesives, or the like. When the adhesive isaggressive in bonding the treated paper substrates together, preferablythey are used in conjunction with a release coating to preferentiallyseparate the sheets without tearing. Alternatively, the adhesive isselected to be non-aggressive such that the adhesive bond fails beforethe paper substrate tears or is damaged. Adhesives may be rendered lessaggressive through a non-tacky filler, including filling withfragrance-containing microcapsules. Microcapsule-containing adhesivesmay fail by fracture of the microcapsule, which results in delivery ofthe fragrance contained in the microcapsule.

An additional alternative adhesive that may be selected for adheringtreated paper sheet(s) together to form the enclosed cavity is arepositionable adhesive, such as disclosed in U.S. Pat. No. 3,691,140 toSilver. In this embodiment, the sampler could be opened without damageto the paper sheet(s), the fragrance sampled and the sampler could bereclosed for subsequent reopening to sample remaining fragrance at alater time.

The ink to be used in the present invention is preferably a standardprinting ink available in the industry. Preferably, the selection of inkis matched with the selection of volatile liquid containment treatmentto be used such that the combination has sufficient cohesive andadhesive strength to remain on the paper without splitting off. This isparticularly important in the sampler format where the microcapsules areadhered to the substrate and cover sheet, and are ruptured upon removalof the cover sheet. Cohesive or adhesive failure of the underlying inkin this format could result in absolute failure of delivery of thefragrance.

The binder material used for adhering the microcapsules to the substratepaper, or the cover paper to the substrate paper may be any appropriatepressure sensitive, water or solvent soluble, or thermally activatableadhesive. Appropriate materials include polyurethanes, polyacrylates,polyvinyl resins, polyamides, polyesters, polyolefins, gum arabic,gelatin and the like. The binder material used for adhering themicrocapsules to the substrate paper may optionally also act as theadhesive for adhering the cover paper to the substrate paper. There isgenerally no need for a gap between the fragrance-containing portion ofthe enclosed cavity and the adhesive that defines one of the edges ofthe enclosed cavity.

Alternative configurations of the microcapsules within the cavity may beutilized, depending on the desired final product. Fragrance samplerspresently are provided in several alternative formats. The first formatis where the cover sheet of paper is adhered to the substrate sheet ofpaper by a binder material provided with the microcapsules. In thisformat, the microcapsules are strongly bonded to the paper, so that whenthe cover sheet is removed from the substrate sheet, the microcapsulesare ruptured and the fragrance is released. In a second format, themicrocapsules are loosely associated with the substrate sheet, and whenthe cover sheet is removed, the microcapsules are available to be pickedup by the user and applied to any location, usually by the finger. Inyet another format, the microcapsules are lightly bound to the substratesheet by a binder material, and may be removed by light finger pressure.An additional format is a combination of one or more of the above, wherethe user receives an initial burst of fragrance upon removal of thecover sheet and rupture of the bound microcapsules and is still able topick up microcapsules from the paper to apply to any desired location.

In addition to microcapsules being disposed within the enclosed cavity,other sources of fragrance may be provided in the present sampler. Forexample, free fragrance oil or materials that deliver fragrance oil in amanner other than through traditional encapsulation may be providedtogether with the microcapsules for enhanced fragrance delivery. Anexample of an alternative means for delivering fragrance oil is byadsorbing the fragrance oil on particles. Preferably, the particles havea large amount of surface area to provide sites for absorbing thefragrance oil. An example of such a particle is talc. Another example ofparticles with a large amount of surface area are polymeric particlesformed in the presence of incompatible materials that are later removedto provide particles having interstices to take up fragrance oil.Alternatively, the polymer of the particle may be selected such that itis swollen by the fragrance oil, thereby acting as a vehicle fordelivery of fragrance oil from a device of the present invention.

In a typical manufacturing operation, the paper is first printed withthe ink as desired. The ink is then dried in-line by passing through anoven. Volatile liquid containment treatment is then applied to thepaper, and allowed to cure as appropriate for the material selected.Curing may optionally be accelerated by passing the paper through asecond oven. Optional anchoring layers for anchoring the microcapsulesto the substrate may be applied and dried at this point. Microcapsulesare then applied to the paper, preferably in a water-based slurry. Atreated cover sheet is then provided over the microcapsules. The coversheet may be a separate paper, or may be provided by folding over of thesubstrate sheet to overlie the microcapsules. It has been found that anadditional drying step is not usually required at this stage to preparea satisfactory product.

The following examples are provided for purposes of illustration only,and are not intended to be limiting of the scope of the invention in anyway.

EXAMPLE 1

In the following example, a fragrance oil was encapsulated by theprocess described in Example 20 of U.S. Pat. No. 3,516,941. Theresulting capsules had a mean diameter of about 20 micrometers and anestimated payload of 85% by volume (ratio of oil to total capsulevolume.) The microcapsules were washed with cold tap water, filtered,and reslurried to 40% solids.

    ______________________________________                                        Component          Dry Weight Wet Weight                                      ______________________________________                                        Microcapsules (40% solids)                                                                       1215.50    3038.75                                         Klucel MF (added as a 3.3%                                                                       6.50       197.00                                          predissolved solution)                                                        Superpearl (pearlescent pigment                                                                  78.0       78.0                                            obtained from Flamenco)                                                       ______________________________________                                    

This mixture was diluted with water to 36.7% solids, with a resultingviscosity of 700 cps. The slurry was thoroughly mixed and passed througha 125 micron screen to remove large particles or agglomerates.

The volatile liquid containment treatment (PVA treatment) solution wasprepared by predissolving the Airvol 523 in water to 14% solids. Theglyoxal, ammonium chloride and water were added and thoroughly mixedjust prior to coating.

    ______________________________________                                        Component        Dry Weight  Wet Weight                                       ______________________________________                                        Airvol 523 polyvinyl alcohol                                                                   812.25      5801.8                                           Glyoxal           97.85       244.6                                           Ammonium chloride                                                                               40.00        40.00                                                           950.10      6086.4                                           Water                         890.26                                                           332.13       3016.27                                         ______________________________________                                    

Samplers were produced at Japs Olson Printing Co. on their M-80-5 Harrisheat set web off-set printing press at a speed of 200 feet per minute.The Warrenflo 70 pound C2S paper was printed with varnish (Arroweb HSOraprint high gloss varnish) and dried in the first oven. The PVAtreatment described above was applied over the printing just prior to asecond oven at a variety of treatment weights from 0.60 to 1.40 poundsper 1300 square feet. The treatment was dried and crosslinked at a webtemperature of 235° F. An adhesive perimeter of standard envelope glue(Craigbond 3822P water-based business form adhesive) was applied overthe varnish and PVA treatment. The microcapsule/pigment slurry was thencoated over the crosslinked polyvinyl alcohol at 3.5 pounds per 1300square feet as shown in FIG. 8. The paper was folded so that a treatedportion of the paper covered the microcapsules, and was allowed to dryat ambient conditions for 72 hours. After drying and opening the sample,the microcapsules could easily be removed for application to the skin byrubbing with a finger tip.

The reduction in detectable volatile organic liquid capsule fillmaterial after crushing of the microcapsules without opening of thesampler was evaluated using gas chromatography as follows.

FRAGRANCE EMISSION RATIO TEST

The sample is triggered by pinch rolling the sampler once on each side,leaving an uncrushed margin at each end to avoid extruding the capsulefill material through the end of the sampler.

Two crushed unopened samples are immediately placed in a containerprovided with an inlet and an outlet to allow purging of the containerwith nitrogen. An SKC charcoal cartridge (Cat. No. 226-01, SKC Inc.,Eighty Four, Pa.) for collection of volatile organic components isinstalled between the sample-containing box and a flowrator. The box ispurged with nitrogen for 1/2 hr. at 200 ml/min. flow rate. The nitrogenis shut off, the cartridge is opened and the front end charcoal iscarefully emptied into a gas chromatograph sample vial containing 1 μlof decyl acetate internal standard. 1 ml of carbon disulfide is addedand the vial is capped, shaken briefly and analyzed by gaschromatography to determine amounts of volatile organic componentsisolated.

The gas chromatograph is temperature programmed to increase from 50° to300° C. at 5° /min. The column used is a boiling-point column (RestekRt_(x) -1, cross-linked PDMS capillary, 30 m×0.32 mm id, 0.25 μm df),50/1 split ration, injector/detector temps 320° C. The standard is 4 μlof oil in 1 ml of acetone, hexane, or methanol, with a 4 μl injection.Attenuation may be 2(1/100) for standard, 0(1/1) for samples.

The results of this test are reported in Table I below as a ratio ofamount of fragrance collected in the gas chromatograph as compared tothe standard described above. Because the amount of capsule fill presentin the box from two samples should be the same for all experiments, thistest is believed to be a good comparison of relative containment offragrance. Some variation due to experimental condition differences isexpected if differing amounts of capsules are fractured in the pinchrolling step.

                  TABLE I                                                         ______________________________________                                        Containment                                                                   Treatment                                                                     Coating Wt.                                                                   lbs/1300 Ft.sup.2                                                                      Test 1.sup.1                                                                          Test 2.sup.2                                                                          Test 3.sup.3                                                                        Test 4.sup.4                                                                        Test 5.sup.5                                                                        Test 6.sup.6                       ______________________________________                                        0.60     4.97    4.78    1.39  0.00  23.99 0                                  0.80     3.26    2.64    2.10  1.89  64.26 15.57                              1.00     3.87    3.19    1.13  0.91  49.57 17.81                              1.20     2.25    1.20    3.55  2.80  48.64 19.22                              1.40     3.05    1.40    2.80  2.14  29.83 4.93                               0.00     25.21   13.54   0.00  0.00  0.00  0.00                               ______________________________________                                         .sup.1 Test 1 represents the percent of fragrance leaking through the         paper. Analysis run at time zero after crushing the capsules. Average of      five analyses.                                                                .sup.2 Test 2 represents a certain component (at time about 13 min.)          leaking through the paper. Analysis run at time zero after crushing the       capsules. Average of five analyses. If comparing the amount of leakage on     a sample with no barrier coat to a sample with, for example, 1.2 lbs.         barrier coat, the amount of leakage has been reduced by 25.21 ÷ 2.25      11.2 times.                                                                   .sup.3 Test 3 is analysis of same samples as 1 but after they aged for 16     hours after crushing the capsules. Average of five analyses.                  .sup.4 Test 4 is analysis of same samples as 2 but after they aged for 16     hours after crushing the capsules. In the sample having no barrier coat,      all the fragrance that could be detected by the G.C. has evaporated.          Samples having a barrier coating still show leakage, indicating that the      fragrance is trapped inside the unit.                                         .sup.5 Test 5 is analysis of same sample as 1 but the sample has been         opened to allow all fragrance inside to be detected by the G.C. One           analysis only.                                                                .sup.6 Test 6 is analysis of same sample as 2 but the sample has been         opened to allow all fragrance inside to be detected by the G.C. One           analysis only.                                                           

The fragrance in the sample with no barrier coat had all evaporatedwhile it was sealed. All the other samples, which are sealed sampleswith barrier coat, show a great deal of fragrance still contained in thesamples. In other words, the fragrance was trapped inside the unit andcould not evaporate through the barrier coat. There was also free oilevidence on samples having a barrier coat, while no free oil was evidenton samples having no barrier coat.

Preferably, the amount of fragrance released by the sampler of thepresent invention emits less than one-fifth of the fragrance released bya sampler having no volatile liquid containment treatment as comparedusing the above described FRAGRANCE EMISSION RATIO TEST. Morepreferably, the amount of fragrance released by the sampler of thepresent invention emits less than one-eighth of the fragrance releasedby a sampler having no volatile liquid containment treatment as comparedusing this test.

What is claimed is:
 1. A method of making a sampler for delivery ofmicroencapsulated liquid fragrance material comprisinga) printing asubstrate sheet with release coating, b) applying a volatile liquidcontainment treatment which, when cured, is an organic polymer, to saidsubstrate sheet and overlying at least a portion of said releasecoating, c) allowing said volatile liquid containment treatment to cureto a state so that it is liquid water-stable and organic liquid capsulefill-stable such that said substrate sheet having volatile liquidcontainment treatment thereon allows the transmission of water moisturevapor therethrough, d) applying an adhesive generally overlying the areacorresponding to the release coating and overlying at least a portion ofsaid volatile liquid containment treatment, e) applying microcapsulescomprising microencapsulated organic liquid capsule fill to saidsubstrate sheet such that they are disposed on at least a portion of thevolatile liquid containment treatment, f) folding said substrate sheetso that the adhesive and portions of the substrate sheet define anenclosed cavity having said microcapsules disposed therein.
 2. Themethod of claim 1, wherein said adhesive additionally containsmicrocapsules that comprise microencapsulated organic liquid capsulefill.
 3. The method of claim 1, wherein said organic liquid capsule fillis a fragrance.
 4. The method of claim 1, wherein said cured volatileliquid containment treatment is a crosslinked polymer.
 5. The method ofclaim 1, wherein said microcapsules are strongly bonded to saidsubstrate paper sheet by a binder, so that when the said cavity isopened the microcapsules are ruptured and the fragrance is released. 6.The method of claim 1, wherein said microcapsules are loosely associatedwith the substrate sheet, such that when the cavity is opened themicrocapsules are available to be picked up by a user.
 7. The method ofclaim 1, wherein said microcapsules are lightly bound to the substratesheet by a binder material, such that when the cavity is opened themicrocapsules may be removed by light finger pressure.
 8. The method ofclaim 1, wherein said volatile liquid containment treatment is providedat a treatment weight between about 0.3 lb/1300 sq. ft. and 1.4 lb/1300sq. ft.
 9. The method of claim 1, wherein said volatile liquidcontainment treatment is provided at a treatment weight between about0.5 lb/1300 sq. ft. and 0.9 lb/1300 sq. ft.
 10. The method of claim 1,wherein said cured volatile liquid containment treatment is acrosslinked polyvinyl alcohol polymer.
 11. The method of claim 1,additionally comprising free fragrance oil disposed within said enclosedcavity.
 12. The method of claim 1, additionally comprising a particledisposed within said enclosed cavity, wherein said particle hasfragrance oil adsorbed therein.
 13. The method of claim 1, additionallycomprising a particle disposed within said enclosed cavity, wherein saidparticle is a polymeric particle that is swollen by fragrance oil.